U.S. patent number 11,384,280 [Application Number 17/213,427] was granted by the patent office on 2022-07-12 for adsorption improved water in supercritical co2 encapsulation for improved oil recovery.
This patent grant is currently assigned to SAUDI ARABIAN OIL COMPANY. The grantee listed for this patent is SAUDI ARABIAN OIL COMPANY. Invention is credited to Abdulaziz S. Al-Qasim, Yuguo Wang.
United States Patent |
11,384,280 |
Al-Qasim , et al. |
July 12, 2022 |
Adsorption improved water in supercritical CO2 encapsulation for
improved oil recovery
Abstract
A dispersion of capsules in critical or supercritical carbon
dioxide is provided. The capsules include an aqueous solution
encapsulated by zeolite-templated carbon particles. Also provided
is a method of making a dispersion of aqueous solution capsules.
The method includes providing a medium of critical or supercritical
carbon dioxide, introducing the aqueous solution into the critical
or supercritical carbon dioxide medium, and introducing a
zeolite-templated carbon particle into the critical or
supercritical carbon dioxide medium. Associated methods of using
the disclosed dispersions in hydrocarbon-bearing formations are
also provided.
Inventors: |
Al-Qasim; Abdulaziz S. (Dammam,
SA), Wang; Yuguo (Dhahran, SA) |
Applicant: |
Name |
City |
State |
Country |
Type |
SAUDI ARABIAN OIL COMPANY |
Dhahran |
N/A |
SA |
|
|
Assignee: |
SAUDI ARABIAN OIL COMPANY
(Dhahran, SA)
|
Family
ID: |
1000005592997 |
Appl.
No.: |
17/213,427 |
Filed: |
March 26, 2021 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B82Y
30/00 (20130101); E21B 43/166 (20130101); B82Y
35/00 (20130101); C09K 8/594 (20130101); B82Y
40/00 (20130101); C09K 2208/10 (20130101) |
Current International
Class: |
C09K
8/594 (20060101); E21B 43/16 (20060101); B82Y
30/00 (20110101); B82Y 35/00 (20110101); B82Y
40/00 (20110101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
3008942 |
|
Jun 2017 |
|
CA |
|
2902361 |
|
Aug 2015 |
|
EP |
|
201664611 |
|
Apr 2016 |
|
WO |
|
2016115142 |
|
Jul 2016 |
|
WO |
|
2016205289 |
|
Dec 2016 |
|
WO |
|
WO 2016/205289 |
|
Dec 2016 |
|
WO |
|
2019140340 |
|
Jul 2019 |
|
WO |
|
Other References
Kyakuno, et al., Amorphous water in three-dimensional confinement
of zeolite-templated carbon, Chemical Physics Letters 2013; 571:
54-60 (Year: 2013). cited by examiner .
Anderson et al.; "First-Principles Prediction of Liquid/Liquid
Interfacial Tension", Journal of Chemical Theory and Computation,
vol. 10, Issue 8, May 28, 2014, pp. 3401-3408 (8 pages). cited by
applicant .
Voronina et al., "Physical foaming of fluorinated
ethylene-propylene (FEP) copolymers in supercritical carbon
dioxide: single-film fluropolymer piezoelectrets". Applied Physics
A--Materials Science & Processing, vol. 90, Issue 4, Mar. 2008,
pp. 615-618 (4 pages). cited by applicant .
Zhang, Y et al., "Dissolution of surfactants in supercritical CO2
with co-solvents", Chemical Engineering Research and Design, vol.
94, Feb. 2015, pp. 624-631 (8 pages). cited by applicant .
Rudyk et al., "Supercritical carbon dioxide extraction of oil sand
enhanced by water and alcohols as Co-solvents", Journal of CO2
Utilization, vol. 17, Jan. 2017, pp. 90-98 (9 pages). cited by
applicant .
Jaime Wisniak and Jacob Zabicky, "The Chemistry of Jojoba Oil",
Proceedings of the Sixth International Conference on Jojoba and its
Uses, 1985, pp. 311-322 (7 pages). cited by applicant .
"Graphene properties (A Complete Reference)", Jul. 15, 2021;
Retrieved from the Internet: URL:
http://www.graphene-battery.net/graphene-properties.htm (2 pages).
cited by applicant .
Li et al., "Field and Temperature dependence of intrinsic
diamagnetism in graphene: Theory and experiment", Physical Review
B, vol. 91, Issue 9, Mar. 1, 2015 (5 pages). cited by applicant
.
Shinn et al., "Nuclear Energy Conversion with Stacks of Graphene
Nanocapacitors", Complexity, vol. 18, Issue 3, Oct. 22, 2012, pp.
24-27 (4 pages). cited by applicant .
A.K. Geim and K.S. Novoselov, "The Rise of Graphene", Nature
Materials, vol. 6, Apr. 2007, pp. 1-14 (14 pages). cited by
applicant .
Kawaguchi et al., "Electronic structure and intercalation chemistry
of graphite-like layered material with a composition of BC6N",
Journal of Physics and Chemistry of Solids, vol. 69, Issues 5-6,
May 2008, pp. 1171-1178 (8 pages). cited by applicant .
Lee et al., "A route towards superhydrophobic graphene surfaces:
surface-treated reduced graphene oxide spheres", Journals of
Materials Chemistry A, vol. 1, Issue 25, 2013, pp. 7312-7315 (4
pages). cited by applicant .
Zhang et al., "Biomimetic graphene films and their properties",
Nanoscale, vol. 4, Issue 16, Jun. 6, 2012, pp. 4858-4869 (12
pages). cited by applicant .
Wang et al., "Biomimetic Graphene Surfaces with Superhydrophobicity
and Iridescence", Chemistry an Asian Journal, vol. 7, Issue 2, Feb.
6, 2012, pp. 301-304 (4 pages). cited by applicant .
Zhang et al., "Super-hydrophobic graphene coated polyurethane
(GN@PU) sponge with great oil-water separation perfomance". Applied
Surface Science, vol. 422, Nov. 2017, pp. 116-124 (9 pages). cited
by applicant .
Zengguo Bai and Bin Zhang, "Fabrication of superhydrophobic
reduced-graphene oxide/nickel coating with mechanical durability,
self-cleaning and anticorrosion performance", Nano Materials
Science, vol. 2, Issue 2, Jun. 2020, pp. 151-158 (8 pages). cited
by applicant .
Wang et al., "Recent developments in superhydrophobic graphene and
graphene-related materials: from preparation to potential
applications", Nanoscale, Issue 16, Mar. 12, 2015 (15 pages). cited
by applicant .
Kumari et al., "Corrosion-Resistant Hydrophobic Nanostructured
Ni-Reduced Graphene Oxide Composite Coating with Improved
Mechanical Properties", Journal of Materials Engineering and
Performance, vol. 27, Issue 18, Oct. 23, 2018, pp. 5889-5898 (9
pages). cited by applicant .
Zhang et al., "One-step fabrication of robust superhydrophobic and
superoleophilic surfaces with self-cleaning and oil/water
separation function", Scientific Reports, vol. 8, Mar. 2018, pp.
1-12 (12 pages). cited by applicant .
Boinovich et al., "Origins of Thermodynamically Stable
Superhydrophobicity of Boron Nitride Nanotubes Coatings", Langmuir,
vol. 28, No. 2, Jan. 17, 2012, pp. 1206-1216 (11 pages). cited by
applicant .
Aliev et al., "Superhydrophobic Coatings Based on Boron Nitride
Nanotubes: The Mechanism of Superhydrophobicity and
Self-Regeneration of Highly Hydrophobic Properties",
Nanotechnologies in Russia, vol. 6, Nos. 11-12, Dec. 23, 2011, pp.
723-732 (10 pages). cited by applicant .
Lee et al., "Superhydrophobicity of Boron Nitride Nanotubes Grown
on Silicon Substrates", Langmuir, vol. 25, No. 9, Apr. 8, 2009, pp.
4853-4860 (8 pages). cited by applicant .
Zhou et al., "Superhydrophobic hBN-Regulated Sponges with Excellent
Absorbency Fabricated Using a Green and Facile Method", Scientific
Reports, vol. 7, Mar. 23, 2017, pp. 1-10 (10 pages). cited by
applicant .
Diao et al., "Oil adsorption performance of graphene aerogels",
Journal of Materials Science, vol. 55, Dec. 16, 2019, pp. 4578-4591
(14 pages). cited by applicant .
Petridis et al., "Advanced Low-Cost Separation Techniques in
Interface Science", Elsevier, Ch. 8, vol. 30, 2019, pp. 173-197 (25
pages). cited by applicant .
Ning et al.; "High capacity oil adsorption by graphene capsules";
Nanoscale; Issue 34; Jul. 27, 2017 (5 pages). cited by applicant
.
Chen et al.; "Graphene Sponge as an Efficient and Recyclable Oil
Sorbent"; AIP Conference Proceedings; vol. 1877; Issue 1; Sep. 11,
2017; pp. 030005-1-030005-10 (10 pages). cited by applicant .
Marchesini et al.; "Porous Boron Nitride Materials: Influence of
Structure, Chemistry and Stability on the Adsorption of Organics",
Frontiers in Chemistry; vol. 7; Mar. 2019; pp. 1-9 (9 pages). cited
by applicant .
Li et al.; "Tuning the Chemical Hardness of Boron Nitride
Nanosheets by Doping Carbon for Enhanced Adsorption Capacity", ACS
Omega; vol. 2; Issue 9; Sep. 1, 2017; pp. 5385-5394 (10 pages).
cited by applicant .
J. Luo et al.; "Activated boron nitride ultrathin nanosheets for
enhanced adsorption desulfurization performance" Journal of the
Taiwan Institute of Chemical Engineers; vol. 93; Dec. 2018; pp.
245-252 (8 pages). cited by applicant .
A. K. Mishra and S. Ramaprabhu; "Carbon dioxide adsorption in
graphene sheets"; AIP Advances; vol. 1; Issue 3; Sep. 1, 2011; p.
032152-1-032152-6 (6 pages). cited by applicant .
D. Iruretagoyena et al.; "Adsorption of carbon dioxide on graphene
oxide supported layered double oxides", Adsorption; vol. 20; Dec.
5, 2013; pp. 321-330 (10 pages). cited by applicant .
W Othman et al.; "Adsorption of CO2 on Fe-doped graphene
nano-ribbons: Investigation of transport properties" Journal of
Physics: Conference Series; vol. 869; Jul. 2017 (4 pages). cited by
applicant .
Xu et al.; "The CO2 Storage Capacity of the Intercalated
Diaminoalkane Graphene Oxides: A Combination of Experimental and
Simulation Studies"; Nanoscale Research Letters; vol. 10; Aug. 8,
2015; pp. 1-10 (10 pages). cited by applicant .
Sun et al.; "Charge-Controlled Switchable CO2 Capture on Boron
Nitride Nanomaterials", Journal of the American Chemical Society;
vol. 135; Issue 22; May 2013 (9 pages). cited by applicant .
Li, J et al.; "Activated boron nitride as an effective adsorbent
for metal ions and organic pollutants"; Scientific Reports; vol. 3;
Nov. 13, 2013; pp. 1-7 (7 pages). cited by applicant .
Mao, X et al.; "Metal-free graphene/boron nitride heterointerface
for CO2 reduction: Surface curvature controls catalytic activity
and selectivity"; vol. 2; Issue 1; Jan. 19, 2020; pp. 1-8 (8
pages). cited by applicant .
Chen, S et al.; "Carbon Doping of Hexagonal Boron Nitride Porous
Materials toward CO2 Capture"; Journal of Materials Chemistry A;
Issue 4; 2018; pp. 1-9 (9 pages). cited by applicant .
Coleman, J. N. et al.; "Two-Dimensional Nanosheets Produced by
Liquid Exfoliation of Layered Materials"; Science; vol. 331; Issue
6017; Feb. 4, 2011; pp. 568-571 (4 pages). cited by applicant .
A. Ambrosi and M. Pumera, "Electrochemically Exfoliated Graphene
and Graphene Oxide for Energy Storage and Electrochemistry
Applications"; Chemistry A European Journal; vol. 22; Issue 1; Jan.
4, 2016; pp. 153-159 (7 pages). cited by applicant .
Chen, Z. et al.; "Activated carbons and amine-modified materials
for carbon dioxide capture--a review"; Frontiers of Enviromental
Science & Engineering; vol. 7; Jun. 2013; pp. 326-340 (15
pages). cited by applicant .
Chen, B. et al.; "Atomically homogeneous dispersed ZnO/N-doped
nanoporous carbon composites with enhanced CO2 uptake capacities
and high efficient organic pollutants removal from water"; Carbon;
vol. 95; Aug. 8, 2015; pp. 113-124 (12 pages). cited by applicant
.
Al Otaibi, M. S.; "Post-Synthesis Functionalization of Porous
Organic Polymers for CO2 Capture"; KAUST Research Repository; Jul.
2014; pp. 1-70 (70 pages). cited by applicant .
Dawson, R. et al.; "Nanoporous organic polymer networks"; Progress
in Polymer Science; vol. 37; Issue 4; Apr. 2012; pp. 530-563 (34
pages). cited by applicant .
Maly, K. E.; "Assembly of nanoporous organic materials from
molecular building blocks"; Journal of Materials Chemistry; vol.
19; Issue 13; Jan. 14, 2009; pp. 1781-1787 (7 pages). cited by
applicant .
Jiang, J. and Cooper, A. I.; "Microporous Organic Polymers: Design,
Synthesis, and Function"; Topics in Current Chemistry; vol. 293;
Sep. 1, 2009; pp. 1-33 (33 pages). cited by applicant .
Cote, A. P. et al.; "Porous, Crystalline, Covalent Organic
Frameworks"; Science; vol. 310; Nov. 18, 2005; pp. 1166-1170 (5
pages). cited by applicant .
El-Kaderi, H. M. et al.; "Designed Synthesis of 3D Covalent Organic
Frameworks"; Science; vol. 316; Apr. 13, 2007; pp. 268-272 (5
pages). cited by applicant .
Uribe-Romo, F. J. et al.; "A Crystalline Imine-Linked 3-D Porous
Covalent Organic Framework"; Journal of the American Chemical
Society; vol. 131; pp. 4570-4571 (2 pages). cited by applicant
.
Duncan J. Shaw; "Introduction to Colloid and Surface Chemistry";
Butterworth-Heinemann; Ch. 10; Feb. 24, 1992; pp. 262-276 (15
pages). cited by applicant .
Sun et al.; "Integrating Superwettability within Covalent Organic
Frameworks for Functional Coating"; Chem; vol. 4; Jul. 12, 2018;
pp. 1-14 (14 pages). cited by applicant .
Liu et al.; "A hydrophilic covalent organic framework for
photocatalytic oxidation of benzylamine in water"; Chemical
Communications; Issue 5; Dec. 10, 2019 (5 pages). cited by
applicant .
Hou et al.; "Covalent Organic Framework-Functionalized Magnetic
CuFe2O4/Ag Nanoparticles for the Reduction of 4-Nitrophenol";
Nanomaterials; vol. 10; Issue 3; Mar. 2020; pp. 1-13 (13 pages).
cited by applicant .
Li et al.; "Core-Shell Structured Magnetic Covalent Organic
Framework Nanocomposites forTriclosan and Triclosan Adsorption";
ACS Applied Materials & Interfaces; vol. 11; Jun. 10, 2019; pp.
22492-22500 (9 pages). cited by applicant .
Cai et al.; "Magnetic solid phase extraction and gas
chromatography-mass spectrometrical analysis of sixteen polycyclic
aromatic hydrocarbons"; Journal of Chromatography A; vol. 1406;
Jun. 20, 2015; pp. 40-47 (8 pages). cited by applicant .
Kyakuno et al.; "Amorphous water in three-dimensional confinement
of zeolite-templated carbon"; Chemical Physics Letters; vol. 571;
Apr. 17, 2013; pp. 54-60 (7 pages). cited by applicant .
Jiao et al.; "Water under the Cover: Structures and Thermodynamics
of Water Encapsulated by Graphene"; Scientific Reports; vol. 7;
Sep. 2015; pp. 1-19 (19 pages). cited by applicant .
Samara et al.; "Unconventional oil recovery from AI Sultani tight
rock formations using supercritical CO2"; The Journal of
Supercritical Fluids; vol. 152; Oct. 2019; pp. 1-9 (9 pages). cited
by applicant .
Han et al.; "Superhydrophobic Covalent Organic Frameworks Prepared
via Pore-Surface Modifications for Functional Coatings under Harsh
Conditions"; ACS Applied Materials & Interfaces; vol. 12; Nov.
21, 2019; pp. 2926-2934 (40 pages). cited by applicant .
Xu et al.; "Organic-Inorganic Composite Nanocoatings with
Superhydrophobicity, Good Transparency, and Thermal Stability";
vol. 4; No. 4; Mar. 19, 2010; pp. 2201-2209 (9 pages). cited by
applicant .
Furukawa, H. and Yaghi, O. M.; "Storage of Hydrogen, Methane, and
Carbon Dioxide in Highly Porous Covalent Organic Frameworks for
Clean Energy Applications"; Journal of the American Chemical
Society; vol. 131; Jun. 4, 2009; pp. 8875-8883 (9 pages). cited by
applicant .
Geng et al.; "Covalent Organic Frameworks: Design, Synthesis, and
Functions"; Chemical Reviews; vol. 120; Issue 16; Jan. 22, 2020;
pages CW-DP (20 pages). cited by applicant .
Prakesh et al.; "Spontaneous recovery of superhydrophobicity on
nanotextured surfaces"; Proceedings of the National Academy of
Sciences; vol. 113; No. 20; May 2, 2016; pp. 1-6 (6 pages). cited
by applicant .
Tie et al.; "Organic Media Superwettability: On-Demand Liquid
Separation by Controlling Surface Chemistry"; ASC Applied Materials
& Interfaces; vol. 10; No. 43; Oct. 8, 2018 (27 pages). cited
by applicant .
Liu et al.; "Developments of `Liquid-like` Copolymer Nanocoatings
for Reactive Oil-Repellent Surface"; ACS Nano; vol. 11; No. 2; Feb.
23, 2017; pp. 2248-2256 (9 pages). cited by applicant .
Non-Final Office Action issued in corresponding U.S. Appl. No.
17/213,440 dated Mar. 18, 2022 (27 pages). cited by applicant .
Non-Final Office Action issued in corresponding U.S. Appl. No.
17/213,449 dated Mar. 28, 2022 (27 pages). cited by applicant .
Office Action issued in related U.S. Appl. No. 17/213,411, dated
Apr. 22, 2022 (29 pages). cited by applicant.
|
Primary Examiner: McCracken; Daniel C.
Attorney, Agent or Firm: Osha Bergman Watanabe & Burton
LLP
Claims
What is claimed is:
1. A composition of matter comprising: a dispersion of capsules in
critical or supercritical carbon dioxide, the capsules comprising
an aqueous solution encapsulated by zeolite-templated carbon
particles.
2. The composition of claim 1, where the capsules have an aqueous
solution diameter in a range of from about 10 nm to 100 .mu.m.
3. The composition of claim 1, where the zeolite-templated carbon
particles have a particle size in a range of from about 10 to 200
nm.
4. The composition of claim 1, where the zeolite-templated carbon
particles are hydrophobic.
5. The composition of claim 1, where the capsules have a diameter
in a range of from about 10 nm to 100 .mu.m.
6. The composition of claim 1, where the dispersion comprises in a
range of from about 60 to 70 vol. % of the aqueous solution.
7. The composition of claim 1, where the dispersion comprises up to
5.0 wt. % of the zeolite-templated carbon particles.
8. The composition of claim 1, where the dispersion has a bulk
density in a range of from about 0.9 to 1.1 g/mL.
9. A method of making a dispersion of aqueous solution capsules,
the method comprising: providing a medium of critical or
supercritical carbon dioxide; introducing the aqueous solution into
the critical or supercritical carbon dioxide medium; and
introducing a zeolite-templated carbon particle into the critical
or supercritical carbon dioxide medium.
10. The method of claim 9, where the aqueous solution is introduced
into the critical or supercritical carbon dioxide medium via a pump
configured to introduce fluids at a temperature and pressure
greater than a temperature of the critical or supercritical carbon
dioxide medium and a pressure greater than a pressure of the
critical or supercritical carbon dioxide medium.
11. The method of claim 9, where the aqueous solution and the
zeolite templated carbon particle are introduced into the critical
or supercritical carbon dioxide medium simultaneously.
12. The method of claim 9, where the aqueous solution is introduced
into the critical or supercritical carbon dioxide medium prior to
the zeolite templated particle being into the critical or
supercritical carbon dioxide medium.
13. The method of claim 9, where the is zeolite templated particle
introduced into the critical or supercritical carbon dioxide medium
prior to the aqueous solution being into the critical or
supercritical carbon dioxide medium.
14. The method of claim 9, where the zeolite-templated carbon
particles have a particle size in a range of from about 10 to 200
nm.
15. The method of claim 9, where the dispersion has a bulk density
in a range of from about 0.9 to 1.1 g/mL.
16. A method of treating a hydrocarbon-bearing formation
comprising: introducing into the hydrocarbon-bearing formation a
dispersion of aqueous solution capsules in a medium of critical or
supercritical carbon dioxide, the aqueous solution capsules
comprising an aqueous solution encapsulated by zeolite-templated
carbon particles.
17. The method of claim 16, where the zeolite-templated carbon
particles have a particle size in a range of from about 10 to 200
nm.
18. The method of claim 16, where the zeolite-templated carbon
particles are hydrophobic.
19. The method of claim 16, where the dispersion comprises in a
range of from about 60 to 70 vol. % of the aqueous solution.
20. The method of claim 16, where the dispersion comprises up to
5.0 wt. % of the zeolite-templated carbon particles.
Description
BACKGROUND
During primary oil recovery, oil inside an underground hydrocarbon
reservoir is driven to the surface (for example, toward the surface
of an oil well) by a pressure difference between the reservoir and
the surface. However, only a fraction of the oil in an underground
hydrocarbon reservoir can be extracted using primary oil recovery.
Thus, a variety of techniques for enhanced oil recovery are
utilized after primary oil recovery to increase the production of
hydrocarbons from hydrocarbon-bearing formations. Some examples of
these techniques include water flooding, chemical flooding, and
supercritical CO.sub.2 injections.
Supercritical CO.sub.2 is an useful fluid for enhanced oil recovery
applications due to its chemical and physical properties as well as
providing the opportunity to introduce a greenhouse gas into a
subterranean area. Supercritical CO.sub.2 is miscible with
hydrocarbons. Thus, when it contacts hydrocarbon fluid in a
reservoir, the fluid is displaced from the rock surfaces and pushed
toward the production well. Additionally, CO.sub.2 may dissolve in
the hydrocarbon fluid, reducing the viscosity of the hydrocarbon
fluid and causing it to swell. This further enhances the ability to
recover hydrocarbons and increase production.
SUMMARY
This summary is provided to introduce a selection of concepts that
are further described in the detailed description. This summary is
not intended to identify key or essential features of the claimed
subject matter, nor is it intended to be used as an aid in limiting
the scope of the claimed subject matter.
In one aspect, embodiments disclosed relate to an aqueous solution
encapsulated by zeolite-templated carbon particles.
In another aspect, embodiments disclosed relate to a dispersion of
capsules in critical or supercritical carbon dioxide, the capsules
comprising an aqueous solution encapsulated by zeolite-templated
carbon particles.
In yet another aspect, embodiments disclosed relate to a method of
making a dispersion of aqueous solution capsules. The method
includes providing a medium of critical or supercritical carbon
dioxide, introducing the aqueous solution into the critical or
supercritical carbon dioxide medium, and introducing a
zeolite-templated carbon particle into the critical or
supercritical carbon dioxide medium.
In another aspect, embodiments disclosed relate to a method of
treating a hydrocarbon-bearing formation. The method includes
introducing into a hydrocarbon-bearing formation a dispersion of
aqueous solution capsules in a medium of critical or supercritical
carbon dioxide. The aqueous solution capsules include an aqueous
solution encapsulated by zeolite-templated carbon particles.
Other aspects and advantages of the claimed subject matter will be
apparent from the following description and the appended
claims.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 shows a simplified schematic of an embodiment capsule useful
for treating hydrocarbon-bearing formations.
FIG. 2 shows a simplified schematic of an embodiment dispersion in
use in a hydrocarbon-bearing formation.
FIG. 3 is a block flow diagram of an embodiment method of making a
dispersion.
FIG. 4 is a simplified schematic of an embodiment hydrocarbon
bearing formation.
DETAILED DESCRIPTION
Carbon dioxide (CO.sub.2) is widely used in flooding processes for
enhanced oil recovery. While it can be effective for oil recovery
due to its affinity for hydrocarbons and its ability to be readily
used in its supercritical state in hydrocarbon-bearing formations,
it suffers from a number of challenges in its use. The density of
CO.sub.2 is less than many of the fluids present in subterranean
formations, including water and the liquid and semi-solid
hydrocarbons. Due to this reduced density, CO.sub.2 has a tendency
to seek upward-directed flow paths in the reservoir as it
progresses away from the injection point and through the reservoir.
This may lead to the introduced CO.sub.2 preferentially bypassing
portions of the reservoir and leaving portions of the reservoir
untreated. This phenomenon is called "gravity override."
The present disclosure relates to compositions and methods for
increasing and maintaining the density of supercritical CO.sub.2 by
adding an aqueous solution encapsulated by zeolite-templated carbon
(ZTC) particles to carbon dioxide in the critical or supercritical
state ("SCCO2"). The SCCO2 dispersions described here provide a
SCCO2 composition with increased density that does not suffer from
the gravity override effect. Such compositions lead to improved
sweep efficiency and enhanced oil recovery of the
hydrocarbon-bearing formation.
Capsules of Aqueous Solution
In one aspect, embodiment capsules disclosed relate to an aqueous
solution encapsulated by zeolite-templated carbon particles. FIG. 1
shows a simplified schematic of an embodiment capsule useful for
treating subterranean formations. FIG. 1 shows a capsule 100 having
an aqueous solution 102 that is encapsulated by zeolite-templated
carbon (ZTC) particles 104. The aqueous solution 102 as given in
capsule 100 has a solution diameter 106. The ZTC particles 104 have
a ZTC particle diameter 108. The capsule 100 has a capsule diameter
110. In the embodiment shown in FIG. 1, the surface 112 of the
aqueous solution 102 is surrounded by a layer of ZTC particles 104
which form an encapsulating shell 114 around the aqueous solution
102 such that it is encapsulated. Several potential shapes of the
ZTC particles 104 are represented, such as spherical 116, pyramidal
118, and cubic 120.
Embodiment capsules include an aqueous solution. For embodiment
capsules, the aqueous solution includes water. The water may
comprise one or more known compositions of water, including
distilled; condensed; filtered or unfiltered fresh surface or
subterranean waters, such as water sourced from lakes, rivers or
aquifers; mineral waters; gray water; run-off, storm or waste
water; potable or non-potable waters; brackish waters; synthetic or
natural sea waters; synthetic or natural brines; formation waters;
production water; and combinations thereof.
In some embodiments, within the embodiment capsule the aqueous
solution is in the form of a liquid, for example, a droplet or
sphere. In such embodiments, the solution diameter may have a range
of from about 10 nm (nanometers) to about 100 .mu.m (micrometers),
meaning the solution diameters have a D.sub.1 of about 10 nm and a
D.sub.99 of about 100 .mu.m. In some embodiments, the solution
diameter may have a range of from about 10 nm to 200 nm. In other
embodiments, the solution diameter may have a range of from about
10 .mu.m to 100 .mu.m. A D.sub.1 value means that 1% of the
solution diameters have a diameter of less than the D.sub.1 value.
A D.sub.99 value means that 99% of the solution diameters have a
diameter of less than the D.sub.99 value.
Embodiment capsules also include a zeolite-templated carbon (ZTC)
particle. In some such embodiments, the zeolite-templated carbon
particle comprises zeolite-templated carbon (ZTC). The
zeolite-templated carbon is made of carbon residue from the
reduction of one or more olefin compounds in a zeolite structure,
forming a 3-dimensional (3D) carbon matrix.
The zeolite-templated carbon particles may be made by a method that
includes introducing an organic precursor gas made of an organic
precursor for a chemical vapor deposition (CVD) period to a
crystalline zeolite that is maintained at a CVD temperature such
that the carbon-zeolite composite forms. The introduced organic
precursor adsorbs via CVD into the crystalline zeolite. The organic
precursor converts into carbon within the crystalline zeolite.
Useful organic precursors for such a process may include propylene,
ethanol and acetylene. The carbon within the crystalline zeolite
forms a carbon template of the internal void structure of the
zeolite. The zeolite templated carbon therefore takes the shape of
a negative replica of the crystalline zeolite on a matrix scale.
The method includes introducing a non-reactive gas for a thermal
treatment period to the carbon-zeolite composite maintained at a
thermal treatment temperature such that a thermally-treated
carbon-zeolite composite forms. The carbon template of the zeolite
within the crystalline zeolite converts into a thermally-treated
carbon template of the zeolite. The method includes introducing an
aqueous strong mineral acid mixture to the thermally-treated
carbon-zeolite composite such that the zeolite templated carbon
(ZTC) is freed from the zeolite structure. Additional details
regarding the ZTC particles disclosed here may be found in U.S.
Pat. No. 9,604,194, which is incorporated by reference in its
entirety.
In other such embodiments, the previously-described ZTC particles
comprise functionalized ZTC particles. In such embodiments, the ZTC
particles may be functionalized with amines, hydroxyl groups,
carboxylic acid groups, and combinations thereof, in order to
increase their affinity for supercritical CO.sub.2.
In other such embodiments, the previously-described ZTC particle
comprises doped ZTC particles. In some embodiments, the dopant for
the ZTC particles is selected from the group consisting of oxygen,
nitrogen, sulfur, iron, zinc, and combinations thereof. The use of
such dopants may allow for the tuning of the degree of
hydrophobicity of the doped ZTC particles.
On the macro-scale, embodiment zeolite-templated carbon particles
may be any appropriate shape useful for encapsulating aqueous
solutions. For example, as shown in FIG. 1, ZTC particles are shown
as spherical (116), cubic (120), and pyramidal (118); however,
geometric and non-geometric configurations are not limited except
as to provide for an encapsulating surface for the aqueous
solution.
Embodiment zeolite-templated carbon particles may be any
appropriate size for encapsulating aqueous solutions. Based upon
the configuration or geometry of the form of the ZTC particle, the
particle size may be determined by a center-traversing axis
parallel with its longest length. So, for example, a sphere may be
measured by its diameter; a cube by its diagonal. In some
embodiments, the zeolite-templated carbon particles have a particle
size in a range of from about 10 to about 200 nm, meaning the ZTCs
have a D.sub.1 of about 10 nm and a D.sub.99 of about 200 nm. A
D.sub.1 value means that 1% of the ZTC particles have a diameter of
less than the D.sub.1 value. A D.sub.99 value means that 99% of the
particles have a diameter of less than the D.sub.99 value.
In some embodiments, the zeolite-templated carbon particles are
hydrophobic. In such embodiments, the water contact angle of
embodiment ZTC particles is from about 90.degree. to about
180.degree.. In some embodiments, the water contact angle of
embodiment ZTC particles is less than 150.degree., such as less
than 120.degree..
In some embodiments, the density of the zeolite-templated carbon
particles is the same or greater than the density of water. In such
embodiments, the density of water is from about 1.0 to 1.2 g/mL
(grams per milliliter), generally corresponding to the density of
water under formation conditions.
As described, embodiment capsules include an aqueous solution that
is encapsulated by ZTC particles. The aqueous solution is
surrounded by the ZTC particles and does not disperse into the
medium hosting the capsules. In embodiment capsules, the aqueous
solution and the ZTC particles are as previously described.
In some embodiments, capsules have a capsule size range, which is
effectively the diameter of the capsule, from about a few
nanometers to a few millimeters. In such embodiments, the capsule
diameter may have a range of from about 10 nm (nanometers) to about
100 .mu.m (micrometers), meaning the capsules have a D.sub.1 of
about 10 nm and a D.sub.99 of about 100 .mu.m. In some embodiments,
the capsule diameter may have a range of from about 10 nm to 200
nm. In other embodiments, the capsule diameter may have a range of
from about 10 .mu.m to 100 .mu.m. The capsule size range for a
given embodiment capsule should be approximately the same in all
directions of the roughly spherical shape; however, variations in
configuration between a given ZTC particle and another may provide
some statistically insignificant differences in determined capsule
size range based on one diameter versus another.
Embodiment capsules have a density in a range of from about 0.9 to
about 1.2 g/mL.
Dispersion of Capsules in Super/Critical Co.sub.2
In another aspect, embodiments disclosed relate to a dispersion of
the embodiment capsules previously described. FIG. 2 shows a
simplified schematic of an embodiment dispersion in use in a
hydrocarbon-bearing formation. A hydrocarbon-bearing formation 200
has pores 206 throughout. An embodiment dispersion within pores 206
may include CO.sub.2 in the critical or supercritical state
("SCCO2") 202 and capsules 204. Arrows (not labeled) show the
direction of flow of the embodiment dispersion through the
hydrocarbon-bearing formation.
In embodiment dispersions, a medium of SCCO2 suspends the
prior-discussed embodiment capsules. The critical temperature for
carbon dioxide is approximately 31.1.degree. C.; the critical
pressure is approximately 8.38 MPa (megapascals). In some
embodiment dispersions, the carbon dioxide is in a critical state.
In some other embodiment dispersions, the carbon dioxide is in a
supercritical state. Embodiment dispersions may include SCCO2 in a
temperature range of from about 50.degree. C. to about 100.degree.
C. Embodiment dispersions may include SCCO2 in a pressure range of
from about 1500 psi (pounds per square inch) to about 5000 psi.
In some embodiment dispersions, the carbon dioxide medium may have
a purity of at or greater than 90%. The purity of the carbon
dioxide is determined before introduction of the capsules into the
embodiment dispersion, the introduction of water into the carbon
dioxide, or the introduction of the carbon dioxide into a
subterranean formation, as any contact may introduce external
impurities into the critical or supercritical carbon dioxide. In
some embodiment dispersions, the carbon dioxide medium may have a
density in a range of from about 0.8 to 0.9 g/mL.
Embodiment dispersions also include capsules as previously
described. The capsules are stable in the SCCO2 environment. The
ZTC particle and aqueous solution do not physically or chemically
degrade or disassociate due to the presence of the SCCO2.
Embodiment dispersions may include a percent volume of water as
compared to the total volume of water and SCCO2. Embodiment
dispersions may include from about 60 to 70 vol. % of water. A
greater water content contributes to an increased density of
embodiment dispersions, as water has a greater density than SCCO2
at formation conditions.
Embodiment dispersions may include any suitable amount of ZTC
particles. In some embodiments, dispersions may include up to 5.0
wt. % of ZTC particles in terms of the total weight of the
dispersion. Embodiment dispersions may have a lower limit of about
1.0, 1.5, 2.0, or 2.5 wt. % ZTC, and an upper limit of about 5.0,
4.5, 4.0, 3.5, or 3.0 wt. % ZTC, where any lower limit may be used
in combination with any mathematically compatible upper limit.
Embodiment dispersions may have a bulk density suitable for
mitigating gravity override. Such dispersions may have a bulk
density of from about 0.9 to 1.1 g/mL at formation conditions.
Embodiment dispersions may include in a range of from about 50 to
70 vol. % of embodiment capsules.
Method of Forming a Dispersion
In another aspect, embodiments disclosed here relate to a method of
making the previously-described dispersion. FIG. 3 is a block flow
diagram of an embodiment method of making a dispersion 300.
The method 300 may include providing a medium of critical or
supercritical carbon dioxide 302. In some embodiments, providing
the medium may include introducing SCCO2 into a subterranean
formation. In such cases, the dispersion may be produced in situ,
that is, within the formation to be treated with the dispersion. As
such, the treatment of the formation and the creation of the
dispersion occur virtually simultaneously. In other embodiments,
the dispersion is fabricated outside of a subterranean formation,
such as on the surface or in a production facility.
The method 300 may include introducing water into the SCCO2 such
that an emulsion of water in CO.sub.2 forms 304. Embodiment SCCO2
may be in a temperature in in a range of from about 50.degree. C.
to about 100.degree. C. and a pressure in a range of from about
1500 psi to about 5000 psi when water is introduced. The water may
be introduced to SCCO2 by any suitable means in which the
previously described temperatures and pressures may be maintained.
For example, the water may be introduced by a pump configured to
introduce fluids at a temperature and pressure greater than the
temperature and pressure of the SCCO2, such by using a high
pressure syringe pump. The water/SCCO2 may then be mixed using
vigorous stirring to form am emulsion. If ZTC particles are already
present in the CO.sub.2 as a dispersion, then the ZTC particles
encapsulate the aqueous solution and the dispersion forms.
Upon introducing an aqueous solution into a SCCO2 medium, an
emulsion of water droplets in SCCO2 may be formed. However, such
emulsions may not be stable for extended periods because water and
SCCO2 naturally separate due to differences in polarity of the two
fluids.
The method 300 may include introducing ZTC particles into the SCCO2
306. The SCCO2 medium in embodiment dispersions may be in a
temperature in a range of from about 50.degree. C. to about
100.degree. C. and a pressure in a range of from about 1500 psi to
about 5000 psi when ZTC particles are added. Embodiment ZTC
particles may be added to embodiment dispersions as a dry powder.
Embodiment ZTC particles may be added to the CO.sub.2 medium under
vigorous stirring to evenly disperse the ZTC particles. The
dispersion may then be stirred for about 30 to 60 minutes.
In some embodiments, the water is added to the SCCO2 prior to the
addition of the ZTC particles to the SCCO2. If water is present in
the SCCO2 medium and an emulsion is already present, the embodiment
dispersion may immediately form. The zeolite-templated carbon
particles described previously may be provided to the emulsion to
encapsulate aqueous solution present, thereby mitigating the
polarity difference, stabilizing the aqueous solution in the SCCO2
medium, and forming the dispersion from the emulsion of water and
SCCO2. In some embodiments, the ZTC particles are added to the
SCCO2 prior to the addition of the water to the SCCO2. If the
aqueous solution is not present in the SCCO2 medium, then a
dispersion of ZTC particles in the SCCO2 is formed. In some
embodiments, the water and ZTC particles may be introduced to the
SCCO2 medium simultaneously.
When introduced into an aqueous solution in SCCO2 emulsion,
hydrophobic particles, such as the previously-described
zeolite-templated carbon particles, may collect at the interfaces
between the aqueous solution and the SCCO2, if water is already
present in the SCCO2 medium. If water is not present, the ZTC
particles will likely be distributed fairly evenly throughout the
SCCO2 medium until water is present. When the aqueous solution is
introduced, however, the ZTC particles will tend to aggregate on
the surface of the aqueous solution even though they are
hydrophobic. As the zeolite-templated carbon particles collect at
the aqueous/SCCO2 interface, a layer of ZTC particles aggregate
around the aqueous solution, as shown in FIG. 1. This ZTC layer
serves to encapsulate the aqueous solution.
Although not wanting to be bound by theory, it is believed that due
to the hydrophobic nature of the embodiments of the
zeolite-templated carbon particles, Van der Walls forces between
the CO.sub.2 molecules in the SCCO2 and surfaces of the
zeolite-templated carbon particles may be strong. This may have the
effect of CO.sub.2 molecules adsorbing to surfaces of the
zeolite-templated carbon particles at SCCO2 conditions. As such,
CO.sub.2 molecules may pack more tightly near the surface of a
capsule as compared to molecules in the bulk SCCO2 medium. This may
result in an increase in the bulk density of SCCO2/capsule
dispersion, which will mitigate the gravity override issue when in
use in a formation or reservoir.
Method of Use in a Hydrocarbon-Bearing Formation
In another aspect, embodiments disclosed here relate to a method of
using the previously-described embodiment dispersion in a
hydrocarbon-bearing formation. As shown in FIG. 2, the embodiment
dispersion comprising the embodiment capsules are shown traversing
the pore structure of a reservoir.
As shown in FIG. 3, an embodiment method may include introducing
the previously-described embodiment dispersion that comprises the
embodiment capsules in SCCO2 into a subterranean formation, such as
a hydrocarbon-bearing formation 308. Embodiment methods may include
introducing a previously-formed embodiment dispersion having the
previously-described embodiment capsules into a subterranean
formation. In other embodiments, components of the dispersion may
be introduced separately, meaning that the SCCO2, aqueous solution
and ZTC particles may each be introduced separately into the
formation, and embodiment dispersions may be formed in the
subterranean formation in situ. Components of the dispersion may be
added to the formation in any order. If introduced into the
formation separately, the ZTC particles may be added as a dry
powder or they may be suspended in a suitable solvent, such as
crude oil, hydrocarbon fractions, such as naphtha, kerosene or
diesel, or SCCO2. The ZTC particles may also be suspended in water
provided it has surfactants to assist in suspension of the ZTC
particles.
FIG. 4 is a diagram that illustrates a well environment 400 in
accordance with one or more embodiments. Well environment 400
includes a subsurface 410. Subsurface 410 is depicted having a
wellbore wall 411 both extending downhole from a surface 405 into
the subsurface 410 and defining a wellbore 420. The subsurface also
includes target formation 450 to be treated. Target formation 450
has target formation face 455 that fluidly couples target formation
450 with wellbore 420 through wellbore wall 411. In this case,
casing (412) and coiled tubing 413 extend downhole through the
wellbore 420 into the subsurface 410 and towards target formation
450.
With the configuration in FIG. 4, the previously-described
embodiment dispersion that comprises the embodiment capsules in
critical or supercritical carbon dioxide may be introduced into the
subsurface 410 and towards target formation 450 via a pump 417
through the coiled tubing 413. In another embodiment, as previously
described, the dispersion may be formed in situ, meaning components
of the dispersion (CO.sub.2, aqueous solution, ZTC particles) may
be introduced into the subsurface 410 separately via the pump 417
through the coiled tubing 413, forming the dispersion inside the
target formation 450. In such embodiments, multiple pumps may be
used to separately inject components of the dispersion.
Hydrocarbon-bearing formations may include any oleaginous fluid,
such as crude oil, dry gas, wet gas, gas condensates, light
hydrocarbon liquids, tars, and asphalts, and other hydrocarbon
materials. Hydrocarbon-bearing formations may also include aqueous
fluid, such as water and brines. Hydrocarbon-bearing formations may
include formations with pores sizes of from about 100 nm to 100
.mu.m. As such, embodiment capsules have sizes in an appropriate
range to traverse pores of hydrocarbon-bearing formations.
Embodiment dispersions may be appropriate for use in different
types of subterranean formations, such as carbonate, shale,
sandstone and tar sands.
Embodiments of the present disclosure may provide at least one of
the following advantages. As described previously, embodiment
dispersions may have greater density than bulk supercritical
CO.sub.2. As such, embodiment dispersions may not have the gravity
override challenges associated with SCCO2 in enhanced oil recovery
applications. The SCCO2 dispersion may traverse deeper into target
formations to treat portions of the formation that have not been
treated or that have been bypassed. The compositions and methods
disclosed here may result in in higher oil recovery and increased
oil production.
When the word "approximately" or "about" are used, this term may
mean that there can be a variance in value of up to .+-.10%, of up
to 5%, of up to 2%, of up to 1%, of up to 0.5%, of up to 0.1%, or
up to 0.01%.
Although only a few example embodiments have been described in
detail, those skilled in the art will readily appreciate that many
modifications are possible in the example embodiments without
materially departing from the envisioned scope. Accordingly, all
such modifications are intended to be included within the scope of
this disclosure as defined in the following claims. In the claims,
means-plus-function clauses are intended to cover the structures
described as performing the recited function and not only
structural equivalents, but also equivalent structures. Thus,
although a nail and a screw may not be structural equivalents in
that a nail employs a cylindrical surface to secure wooden parts
together, whereas a screw employs a helical surface, in the
environment of fastening wooden parts, a nail and a screw may be
equivalent structures. It is the express intention of the applicant
not to invoke 35 U.S.C. .sctn. 112 (f) for any limitations of any
of the claims, except for those in which the claim expressly uses
the words `means for` together with an associated function.
* * * * *
References